65232-41-9Relevant academic research and scientific papers
Study of the reactivity of organonickel sigma-complexes towards nitriles
Gafurov,Sakhapov,Babaev,Dobrynin,Kurmaz,Metlushka,Rizvanov, I. Kh.,Shaikhutdinova,Sinyashin,Yakhvarov
, p. 254 - 259 (2017/07/11)
The reactivity of organonickel sigma-complexes of type [NiBr(Ar)(bpy)], where Ar = 2,6-dimethylphenyl (Xyl), 2,4,6-trimethylphenyl (Mes), 2,4,6-triisopropylphenyl (Tipp), 2,4,6-tricyclohexylphenyl (Tchp), bpy = 2,2′-bipyridine, towards nitriles (acetonitr
Synthesis of aryl ketones or ketimines by palladium-catalyzed arene C-H addition to nitriles
Zhou, Chengxiang,Larock, Richard C.
, p. 3551 - 3558 (2007/10/03)
The unprecedented palladium-catalyzed C-H addition of arenes to nitriles provides moderate to excellent yields of aryl ketones or the corresponding hindered imines. The addition of a small amount of DMSO increases the yields dramatically. Both intermolecular and intramolecular reactions are successful, although the intramolecular reactions tend to be more sluggish. This novel chemistry is believed to involve palladium-catalyzed C-H activation of the arene by electrophilic aromatic substitution, followed by the unusual carbopalladation of a nitrile. Similar reactions have been successfully developed employing arylboronic acids and nitriles. A concise route to xanthones starting from cheap starting materials has been developed employing this synthetic protocol.
Synthesis of Aryl Ketones by the Pd-Catalyzed C-H Activation of Arenes and Intermolecular Carbopalladation of Nitriles
Zhou, Chengxiang,Larock, Richard C.
, p. 2302 - 2303 (2007/10/03)
The palladium-catalyzed reaction of simple arenes and nitriles provides good to excellent yields of aryl ketones or the corresponding hindered imines. The addition of a small amount of DMSO increases the yields dramatically. Both intermolecular and intramolecular examples of this process are successful. This novel chemistry is believed to involve palladium-catalyzed C?H activation, followed by carbopalladation of the nitrile. Copyright
Experiments to Synthesize a Formal Nitrile Oxide-Benzene Adduct. 1,3-Dipolar Cycloadditions to Bicyclohex-5-ene-2,3-dicarboxylic Anhydride, Dewar Benzene, and 1,4-Cyclohexadiene
Christl, Manfred,Mattauch, Brigitte
, p. 4203 - 4223 (2007/10/02)
The reaction of bicyclohex-5-ene-2,3-dicarboxylic anhydride (7) with benzonitrile oxide, 2,4,6-trimethylbenzonitrile oxide, diphenylnitrile imine, diazomethane, tetrachloro-o-quinone, and tetrachlorothiophene 1,1-dioxide furnished the Δ2-isoxazolines 8a, 8b, the Δ2-pyrazoline 8c, the Δ1-pyrazoline 10d, the α-diketone 11, and the tetrachloro-1,3-cyclohexadiene derivative 12, respectively. - Dewar benzene (16) was prepared via the urazole 13, obtained from benzvalene by the addition of 4-methyl-4H-1,2,4-triazole-3,5-dione, and the azo compound 17, from which nitrogen gas eliminated by photolysis.The 1:1 adducts 6a, 6b, 20, and 21 as well as the 1:2 adducts 18a, 18b, 19b, 22, and 23, respectively, were formed on treatment of 16 with benzonitrile oxide, 2,4,6-trimethylbenzonitrile oxide, and diazomethane.At 120 deg C the 1:1 adduct 6b decomposed to give benzene and the 1:2 adducts 18b, 19b, probably via the intermediate 1b, which was the target molecule of this investigation.If the thermolysis was carried out in the presence of dimethyl fumarate, 18b, 19b were no longer observed and the dimethyl Δ2-isoxazoline-3,4-dicarboxylate 24 was obtained instead. - 1,4-Cyclohexadiene reacted with benzonitrile oxide and 2,4,6-trimethylbenzonitrile oxide to provide the 1:1 adducts 25 and the 1:2 adducts 26 - 28.The thermal decomposition of 25b resulted in the formation of mesitylphenylketimine (31).A 3:1 mixture of the dibromides 32 and 33 was obtained on addition of bromine to 25a.Elimination of hydrogen bromide from 32 was effected by diazabicycloundecane with benzene and diphenylfuroxan (35) being the products and the formal benzene adduct 1a the most likely intermediate.Compound 32 was tr ansformed into the spiran 36 by using the stronger base potassium tert-butoxide.
